CS189691A3 - 1/(o-(cyclopropylcarbonyl)phenyl)sulfamoyl/ -3-4- (4,6-dimethoxy-2-pyrimidinyl) urea, process of its preparation and herbicides based thereon - Google Patents

Description

V. 1 '(1' - (cyclopropylcarbonyl) phenyl) sulfamoyl] -3- (4,6-dimethoxy-2-

pyrimidinyl) urea, a process for its preparation and herbicidal compositions. .Alpha., .Alpha., .Alpha., .Alpha., 4 '. -Λ ,! 'Λ

Ji - * + β '

Technical field

The present invention relates to 1 - [(o- (cyclopropylcarbonyl) phenyl) sulfomoyl] -3- (4,6-dimethoxy-2-pyrimidinyl) urea, a process for the production of herbicidal compositions thereof. The urea is found to be a highly potent herbicidal agent suitable for selectively controlling unwanted weeds in the presence of crops. '. . The invention also relates to 1 - {o - (cyclopropylcarbonyl) phenyl} sulfamoyl / -3- (4,6-dimethoxy-2-pyrimidyl) urea herbicide, which exhibits at least twice the safety in the application of broadleaf weeds and grasses, growing in the presence of cereals, such as barley, wheat, oats, rye rice and at least fourfold safety when used to suppress broadleaf, willow, and sedge in the presence of rice plants planted on the back. foam fields. . ; The invention also relates to a method of selectively controlling undesirable vegetation in the presence of cereals using 1 - [(o- (cyclopropylcarbonyl) phenyl) sulfamoyl] -3- (4,6-dimethoxy-2-pyrimidinyl) -urea. Among the undesirable species of weed plants that can be suppressed by the above-mentioned sulfamoylurea derivative, cassia (Cassia obtusifolita) may be mentioned; annual sedge; yearly choroid; Common Flatsedge (Cyperus esculentus); cyperus serotinus; arrowhead (Sagittaria pygmaea); Cyperusrotundus; Crisp (Scirpus spp.); (Ipomoea spp.) acacia (Sesbania exalta).

The invention also relates to a process for the preparation of 1 - [(o- (cyclopropylcarbonyl) phenylsulfamoyl] -3- (4,6-dimethoxy-2-pyrimidinyl) urea 2

The unique property of the sulfamoyl urea derivative mentioned above is its high safety when used against

In particular, rice, and especially rice plants planted with ha: yellow. "k-. in '^ foam fields.'

SUMMARY OF THE INVENTION

According to the invention, 1 - [(o- (cyclopropylcarbonyl) phenyl) sulfamoyl] -3- (4,6-dimethoxy-2-pyrimidinyl) urea can be prepared by reaction of 2-amino-4,6-dimethoxypyrimidine with chlorosulfonyl isocyanate in the presence of the methylene chloride is then treated with o-aminophenyl cyclopropyl ketone and triethylamine in the presence of methylene chloride. .

The discovery that selectivity in the presence of cereals, in particular, occurs upon introduction of cyclopropyl to a carbonyl functional group attached to the phenyl ring of the sulfamoyl-urea derivative is unexpected. Surprisingly, it has been found that this substitution provides selective control of various unwanted weed plants, particularly broadleaf weeds and barley in the presence of barley, wheat, oats and rye, as well as barley. In addition, it has also been found that with the aforementioned compound, the development and / or retention of several unwanted grass plants, such as, can be very advantageously retarded. »A chicken leg. When these weed plants come into contact with 1-7 (o-cyclopropylcarbonyl) phenyl) sulfamoyl] -3- (4,6-dimethoxy-2-pyrimidinyl) urea in the treatment of crops to suppress broadleaf weeds and sedges in they are often even killed. In practice, the sulfamoyl urea of the present invention can be applied to crops in the form of a solid or liquid herbicidal composition containing a herbicidally effective amount of sulfamoyl urea dispersed in an inert solid or liquid carrier. The compositions can be applied preemergence or postemergence. however, it is usually most effective to apply these agents, preferably granulates, pre-emergence after transplanting 3 rice plants. Thus, the compositions of the invention are applied to the soil or to the flooded water after transplanting the rice plants, but before or after the emergence of weed plants. It is also possible to apply the composition to rice plants before transplanting.

Herbicidal. by means of. The present invention can also be applied to the leaf, in the case of cereals, to the emergence of weeds, making it highly suitable for use in weed control in barley, wheat, oat, rye and directly sown rice. 1 - [(o- (cyclopropylcarbonyl) phenyl) sulfamoyl] -3- (4,6-dimethoxy-2-pyrimidinyl) urea can be " treated " to a wettable powder, liquid suspension Concentrates or granules The wettable powder can be obtained by grinding 65% by weight of 1 - [(o - (cyclopropylcarbonyl) phenyl) sulfamoyl] -3- (4, 6-dimethox-2-yl). % of sodium sulfonate-modified kraft in urea in a vial of 6.0% by weight of sodium sulfonate-modified kraft. lignin, which does not contain sugar (dispersant), 3.0% w / w anionic surfactant, such as dioctyl sodium sulfosuccinate (surfactant), 0.20% w / w silica, 0.10% w / w silicone antifoam agent. Before application to crops and weeds growing> in crops of these crops, the powder is usually dispersed in water and applied as a water spray. the impression of undesirable vegetation, especially broadleaf weeds in the presence of cereals, is usually sufficient to apply a sufficient amount of spray to provide a 1/1 - (o- (cyclopropylcarbonyl) phenyl) sulfamoyl / -3- (4,6, dimethoxy-2-pyrimidinyl) urea 0.016 to 1.0 kg / ha, preferably 0.02 to 0.20 kg / ha.

The aforementioned sulfamoyl urea derivative may also be formulated into granular compositions by dissolving or dispersing the active compound in solvents such as acetone, methylene chloride and the like, and sorption granules being applied to the toxic solvent mixture; such as attapulgite granules, 4 montmorillonite, corn bud meal, bentonite, and the like. Usually, the toxicant solution is applied to the granules in such amount; in order to achieve a concentration of the toxic substance in the granules. 20% to 2.0% by weight. Of course, is it possible? The most important factor is the granular absorption capacity of the granules. The granules are usually applied to the soil or water in which the crops grow in an amount to achieve a treatment level of 0.016 to 1.0 kg / ha, preferably about 0.02 to 0.20 kg / ha, based on the toxic compound.

A typical suspension concentrate can be prepared by grinding about 20-60% by weight of sulfamoylurea, 1-5% by weight of sodium condensed naphthalenesulfonic acid, 2-4% by weight of gel forming clay, 2% by weight of propylene glycol, and about 30-55% by weight of water. ?

The suspension concentrate is usually diluted with water in sufficient quantity to be administered to the area in which the crops are applied, to deliver the active ingredient in the amount of 0.016 to 1.0 kg / ha, preferably 0.02 to 0.20 kg / ha, of the treated area.

The invention is illustrated by the following examples. These examples are merely illustrative and are not intended to limit the scope of the invention in any way. EXAMPLES Example 1 Preparation of o-aminophenyl cyclopropyl ketone

To 100 ml of a 1.0 M solution of boron trichloride in methylene chloride and 100 ml of ethylene dichloride was added 9.3 g (0.1 mol) of aniline at 0-5 ° C. After the addition of aniline, 10 g (0.15 mol) of cyclopropylpyridyl cyanide and then 14.4 g (0.11 mol) of aluminum chloride are added in portions. The mixture was allowed to warm to room temperature and placed in a distillation unit. Methylene chloride is removed from the mixture by raining until the temperature in the cooker rises to 70 ° C. The remaining mixture was then refluxed for 18 hours. The reaction mixture is cooled in an ice bath and water is added to the cooled mixture. The water is added in sufficient quantity to dissolve the compound in the mixture, and then the whole is extracted twice with 100 ml of methylene chloride. The organic extracts were combined, dried over anhydrous magnesium sulfate, and evaporated in vacuo to give 9.3 g of yellow oil (70% of actual product by NMR). The reaction can be illustrated by the following "scheme":

Example 2 1 "Preparation of 1 - [(O- (cyclopropylcarbonyl) phenyl) sulfamoyl] -3- (4,6-dimethoxy-2-pyrimidinyl) urea

A solution of 1.78 g (0.0114 mol) of 2-amino-4,6-dimethoxypyrimidine in 50 ml of methylene chloride is cooled to 0.5 ° C in an ice bath. -2-g-O-z-1-a-mol-chloro-sulfonyl-isocyanate. The resulting mixture was stirred for 30 minutes and then a solution of 2.66 g of o-aminophenyl cyclopropyl ketone (70% of actual product, 0.0114 mol) and 2.6 ml of triethylamine (0.0187 mol) in 50 ml of methylene chloride was slowly added. The resulting solution was stirred at ambient temperature for 18 hours (high).

The reaction mixture was evaporated in vacuo and the resulting residue was dissolved in 50 mL of methanol. The pH of the resulting solution is adjusted to pH 1 with 10% hydrochloric acid and the solution is allowed to stand for 6

The resulting white solid precipitate was filtered off and dried. 3.8 g (70%) of the desired product is obtained

Example 3

Rice tolerance in preemergence application, upland conditions #

The tolerance of rice under pre-emergence conditions to the compound of the invention is documented by the following test, in which rice seeds (Tebonnet) are sown in sassafras humus soil containing 1, 5 organic matter, placed in square plastic pots of 10 cm edge. The soil is steam-steamed. Each test is repeated three times. After sowing, the pots are irrigated to achieve field conditions and then sprayed with a laboratory belt sprayer. The test compound is applied in the form of an aqueous-acetone mixture (50: 50 by volume) at a level of treatment of 1.0; 0.5; 0.25; 0.125; 0.063; 0.032; 0.016 and 0.008 kg / ha. The treated pots are then placed on greenhouse shelves where they are sweetened and handled in a conventional greenhouse manner. After 3-4 weeks of treatment, each pot is inspected and herbicidal activity is classified according to visual observation, posture, size, strength, chlorosis, malformation, and overall plant appearance. The following classification system is used:% suppression Meaning (compared to controls, sample) 0 no 'efficiency ..... 0 -' - 1 trace efficiency 1. - 5 · 2. moderate efficacy 6 "15 3 'poor efficacy 16' - 29 4 damage 30 - 44 5 clearly recognizable damage 45 - 64 6 herbicidal efficacy 65 - 79 7 .. good herbicidal efficacy 80 - 90 T" almost complete killing --- Complete killing 100 In this example, the following results are used to refer to the results: 7 - ^ ——————- -, -:: -, -

Abbreviation «Meaning

PE

POST-T

ECH

CYPSE g / ha kg / ha preemergence after planting of cyperus serotinusgrams per hectare per hectare -yy-1-pdk-y-thiocarboxylic acid as indicated below.

Rice selectivity (pre-emergence treatment)

Compound grade herbicidal treatment efficacy (kg / ha); 1 - [(o- (cyclopropylcarbonyl) phenyl) sulfamoyl] -3- (4,6-dimethoxy-2-pyrimidinyl) urea 7 7 5 1 0 0 o by 1.00 0.50 0.25 0.125 0.063 0.032 0.016 0.008 8

The tolerance of rice to the compound of the invention. after application under flooded field conditions? i '. '* ·· - Λ ... - ·'. ”7- * · γ. .. «· / 6 · * -i J i *: ·. ·. . '4' 'Tolerance' of 'planted rice' to the application of herbicide after planting 'sé *' šá áhóvújé as follows: 10-day-old rice plants are planted in loamy-sand soil placed in 9OOg plastic containers with a diameter of 10.5 cm. After transplanting the rice plants, the vessels are flooded with water, the water level being maintained at 1.5 to 3 cm above the soil surface. Three days after transplanting, the selected water-acetone (50: 50 by volume) ) a mixture containing the test compound in an amount corresponding to the treatment with an active ingredient of 1.0, 0.5, 0.25, 0.125, 0.063, 0.032, 0.016, 0.008.kg / ha. to maintain the above-mentioned levels in the containers and otherwise treat them as normal in the glass. both are examined and the herbicidal activity determined according to the above classification system.

Application after transplanting, under flooded field conditions

Compound kg / ha ECH CYPSE rice 1 - / (0- (cyclopropylcar- 1,00 9 9 3) phenyl) sulfamOyl · ./- 0.50 9 9 1 3- (4,6-dimethoxy-2- 0.125 9 9 0 pyrimidinyl) urea 0.063 8 9 0 0.032 8 8 0 0.016 5 8 0 0.008 2 - 0 9

Preemergence weed control under flooded field conditions The preemergence herbicidal efficacy under flooding conditions against eel spurge and cypress Cyperus sherotinus is set out as follows:. .semena ježatky. chicken legs or tubers Cyperus .seřotinus is planted in top 0.5 cm loamy sand soil in 900 g plastic pots with a diameter of 10.5 cm which do not contain any drainage holes. Throughout the experiment, water is introduced into the tads, the level of which is maintained at 1.5 to 3 cm above the soil surface. The test compounds are applied in the form of aqueous acetone mixtures (50:50 by volume) which are pipetted directly into the flood water in an amount to achieve an equivalent treatment level of 1.00; 0.5; O, 25; 0.125, 0.063; 0.032; 0.016; .008 kg / ha. The treated pots are placed on the greenhouse shelves in the greenhouses common. Three to four weeks after the treatment, the test is terminated, each pot is inspected and, according to the above-mentioned, the potency system is determined. ___

The degree of rice-safe treatment ensures weed control λ For the degree of treatment that is safe for rice-treated higher grade (vg / ha) with which herbicidal activity of 0 or 1 is achieved. weed control is considered the lowest treatment level (in g / ha) with which herbicidal efficacy is achieved at 8 or 9. (in g / ha)

Compound 1 - [(cyclopropylcarbonyl) phenyl) sulfamoyl] -3- (4,6-dimethoxy-2-pyrimidinyl) urea

Stage Degree ECH CYPSE treatment treatment degree degree safe safe suppression of rice suppression. for rice PO POST-T 63 500 32 16 10

Boundaries of selectivity. '-λ' i. ·. ; By the selectivity limit is meant the ratio of the rice grade grade (g / ha) and the degree of weed control (g / ha) for each particular weed. /; This value is calculated on the one hand for the rice-refining-safe treatment stage and on the rice-safe treatment level in the pre-emergence treatment. Although rice sepreemergence is not used in rice cultivation under conditions of rice, it is a more extreme method of evaluating the physiological tolerance of rice to the herbicides tested since rice seedlings are exposed to herbicide from the moment of seed germination. selectivity boundary

Compound

Rice POST-TECH CYPSE

Rice PE

ECH CYPSE 1 - [(cyclopropylcarbonylphenyl) sulfamoyl] -3- (4,6-dimethoxy-2-pyrimidinyl) urea i 16 32 2.0 4 Example 4

Suppression of broadleaf weeds and wheat and barley tolerance in post-emergence treatment

The post-emergence herbicidal activity and selectivity of wheat and barley are demonstrated by the following assays: Separate cups containing commercially available artificial greenhouse growth medium (Metromix 350), which contains> peat moss, vermiculite,. sand and activated carbon. The plants are grown in the greenhouse for about two weeks and then sprayed with the selected aqueous-acetone solution of the test compound in an amount such that an equivalent treatment of 0.004 to 2.0 kg / ha is achieved.

The solutions used also contain approximately two molar equivalents of diethylamine per mole equivalent of test compound to increase the solubility of the test compound in the aqueous-acetone solution; , such as alkylaryl polyoxyethylene glycol with free fatty acid and isopropyl alcohol. After spraying, the plants are placed on greenhouse shelves and handled in a manner that is common in greenhouses. After 3-5 weeks after treatment, each cup is inspected and according to the classification system given, in which case the herbicidal activity value is determined? In the cereal tolerance tests, three cups are used for each treatment, and the data represent average hours. replication .._______________. ~ ------

Crops and weeds plants used in these tests

Plodiny Czech name and variety / Rýže Tebonnet

Winter barley, Barberouse Spring barley, Bonanza Winter wheat, FidelPšenice - jaro -, - Katepw.a_ „Fsenice. glassy, Wakooma

Latin name /

Oryza sativaHordeum vulgareHordeúm vulgareTriticum aestivumTriticum aestivum

Triticum aestivum

Weeds

Czech name '; Latin name ECH Gray-footed hedgehog Echinochloa crus-galli CYPSE Cyperus serotinus GALAP Galium aparine STEME Stellaria media TAROF Taraxakum officinale KCHSC Bytel Kochias scoparia VIOAR 'Viola arvensis PAPŠS Papaver sp. MATIN Camomile Matricaria inodora PRUVS. Prunella vulgaris VERSS Veronica sp.

Tolerance of individual cereal species and varieties to postemergency application of 1 - [(o- (cyclopropylcarbonyl) phenylsulfamoyl] -3- (4,6-dimethoxy-2-pyrimidinyl) urea.

Visual evaluation of herbicidal activity based on the above-mentioned classification system

Barley Wheat Wheat Wheat Wheat Wheat winter-winter treatment spring spring kg / ha Barberouse Fidel Wakooma Katpewa Bonanza 2.00 5.3 3.7 3.7 4.0. 5.3? 1.00 4.0: 2.7 3.0 2.3 .4.3 0.500 3.7 2.7 2.3 2.0 4.0 0.250 '2.3 1.7 0.7 1.7 3.7 0.125 1.7 1.0 0.0 1.3 '2.7 0.063 0.7 0.0 0.3 0.0 1.3. 0.032 0.3 0.0 0.0 0.0 0.3 13

Suppression of various species of large-plant postemergence applications> 1 VI ω and H> .PL> 0> o <0> ε © os pH and X c • H • H z E • H m μ> 1 2 an 1 m CM H '-1 - X -> 1 M tn X> 5-1 cn 0 aa £ 4J 0) a Φ i — 1 E Ό Ή 0 Ό and 1 axis <O u ---- ω — o --- ---- Ό) rH H + J Φ · 1 01> <n X Φ [CO rl and -rl CJ> 1 £> i ω 0 M £ X £ c £ U (0> u 5-1 «Mt Q r — 1 -X 2 • ω · ω M: —1 * H and X (0 o -c Φ and m H m X &amp; 4 MX -μ £ • rt 0> N w Λ P s 5- 1 0 w «V Uu ------ - 'Λί cn rH Φ> 1 N and 0 54 aa 0 £ rH <, xu> 1 c 1' M 0 C> £ Φ Φ> U 1 a-μ iH 3 Φ + J XO CPw ι © ι ι mo mo mo mo mo mo mo mo — — — — — — — a a a a a a a a 'oo oo © oo oo oo H' '' '' '' '' H H H H H H - - - - -

Claims (8)

^ 'b J: 1 - (R) (R) (Cyclopropylcarbamoyl) phenyl) sulfamoyl-3-civic acid; fi-di-, • '' Siq-Jr &amp; methoxyl-2-pyrimidinyl) urea. 2. Ortho-aminophenyl cyclopropyl ketone for the preparation of a compound according to claim 1. 3. A method for selectively controlling undesirable vegetation in the presence of cereals, characterized in that the leaves and stems of cereals and undesirable vegetation growing in their presence or in the soil or water containing seeds or other propagation organs are undesirable vegetation in which they produce 1 - (o - (cyclopropylcarbonyl) phenyl) sulfamoyl) -3- (4,6-dimethoxy-2-pyrimidinyl) urea is applied in an amount effective to inhibit this undesirable vegetation. The method according to claim 3, characterized in that the unwanted vegetation is formed by hedgehog, broadleaf weeds and sedge, and the crops are barley, wheat, oats, rye or rice. 5. A process according to claim 3 wherein 1 - [(o- (cyclopropylcarbonyl) phenyl) sulfamoyl] -3- (4,6-dimethoxy-2-pyrimidinyl) urea is applied to crops and undesirable vegetation or soil or water containing seed or other promotional organs of this undesirable vegetation, in an amount of 0.016 to 1.0 kg / ha. 6. A method of selectively suppressing unwanted vegetation in transplanted or seeded cultures of directly growing rice, characterized in that the leaves and stems or the. soil or water containing seeds or other promotional organs of undesirable vegetation applied after transplanting rice or encouraging directly sown rice from soil, herbicidally effective amount of compound of formula ** A method according to claim 6, characterized in that the unwanted vegetation consists of hedgehog, broad-leaved weeds, or sedge. the herbicidal active compound is applied to the leaves of the crop or to the soil or water in the amount of 0.016 to 1.0 kg / ha. __ __ 8_. 2. A method according to claim 6, wherein the compound is flooded with a field and the compound is applied in an amount of from 0.02 to 0%. , 20 kg / ha. 9. A process for the preparation of 1 - [[alpha] - (o-o-oxo-propylcarbonyl) phenyl) sulfamoyl] -3- (4,6-dimethoxy-2-pyrimidinyl) urea, I v. that the 2-amino-4,6-dimethoxypyrimidine is reacted with the chlorophosphate by the isocyanate in the presence. methylene chloride and the reaction mixture thus obtained are treated with ortho-aminophenylcyclopropyl ketone and triethylamine in the presence of methylene chloride. 10. The process of claim 9, wherein about equimolar amounts of 2-amino-4,6-dimethoxypyrimido-7-chloro-2-amino-4,6-dimethoxypyrimido-7-chloro-2-ol are used. 11. A 3-sulfonyl isocyanate, an ortho-aminophenyl cyclopropyl ketone and triethyl i-amine 11. A herbicidal composition comprising an effective amount of 1 - [(o- (cyclopropylcarbonyl) j] phenyl) sulfamoyl) -3- (4,6-dimethoxy-2-pyrimidinyl) urea and an inert carrier; MP-91-91-Ce